Salicyloylamino-anthraquinone pigments

ABSTRACT

Salicyloylamino-anthraquinones are described in which the benzene nucleus of the salicyloyl radical is substituted by an amido group. Preferred pigments of this class are of yellow color with a greenish hue, and are distinguished by particularly good weatherand light-fastness and fastness to solvents.

United States Patent Pugin et al. 1451 Aug. 8, 1972 [54] SALICYLOYLAMINO- ANTHRAQUINONE PIGMENTS [56] References Cited [72] Inventors: Andre Pugin, Grenzacherweg 301, UNITED STATES NT 135322 522 'igf figa f ggf 2,533,178 12/1950 Randall et a1 ..260/326 heimerstrasse 69, both of Basle, all of Switzerland Filed: Sept. 2, 1969 Appl. No.: 854,770

Foreign Application Priority Data Sept. 13, 1968 Switzerland ..13770l68 US. Cl. ..260/326 D, 260/41 C, 260/281, 260/295 T, 260/3475, 260/37 D, 106/23, 106/288 Q Int. Cl. ..C07d 27/52 Field of Search ..260/326 D Primary Examiner-Alex Mazel Assistant Examiner-Joseph A. Narcavage Attorney-Wenderoth, Lind & Ponack ABSTRACT 8 Claims, No Drawings SALlCYLOYLAMINO-ANTHRAQUINONE PIGMENIS DESCRIPTION OF THE INVENTION The present invention concerns new anthraquinone pigments; processes for the production thereof and their application for the pigmenting of high molecular organic material.

It is well known that l-salicylic amidoanthraquinones are suitable as pigments. Pigments of this series are thus known wherein the salicylic acid radical is substituted by chlorine. These pigments usually have a very good fastness to light but the other fastness properties, especially fastness to migration and cross-lacquering, are not good, so that their use in lacquers and plastics is extremely limited.

It was therefore not foreseeable that the anthraquinone pigments, according to the invention, would have the desired properties, at the same time preserving their good fastness to light. The compounds concerned are of the formula I,

IIIHX (I) Ya a wherein from Y, to Y at most four Y-substituents represent chlorine, at most two Y-substituents represent the methyl or the methoxy radical or bromine and of Y Y and Y, at most one substituent represents H,N or aroylNl-l and the remaining Y, Y, represent hydrogen, and whereby X represents the radical of the formula ll,

R: n -o o H wherein n represents 1 or 2 R represents hydrogen and R, represents the acyl radical of the formula Ill,

0 (III) 1 Ba wherein R, represents an alkyl radical having one to four carbon atoms, a monoor binuclear aryl radical, an heterocylic or hydroaromatic radical, or the radical OR, or NHR wherein R. denotes an aromatic or an aliphatic radical having one to four carbon atoms, or R and R, represent, together with the nitrogen atom, an optionally condensed, 5- or 6-membered, cylic dicarbimide radical, and the phenyl radical A can be substituted by halogen, trifluoromethyl, methoxy or alkyl having one to four carbon atoms.

acid

In the compounds of the formula I, one or several of the symbols Y, to Y, can for example represent chlorine or bromine, whereby in particular the 4- chloro, S-chloro, 6, 7-dichloro, 5,6,7,8-tetrachloro and the 2,4-dibromo-substituted anthraquinone compounds are preferred.

The Y-substituents can also represent the methyl or methoxy radical, whereby the Z-rnethyl, 4-methoxy, 4- rnethoxy-S-chloro or the 2-methyI-4-chloroanthraquinone compounds are particularly important. One of the substituents Y,, Y, and Y. can also denote the ---NH,- group, whereby the NH,-group, in its turn, can be substituted by the acyl radical of an optionally substituted benzoic acid, amongst others also by the radical X. Thus in formula I, the anthraquinone radical can contain for example in four-position, the benzioylamino group.

In formula II, the phenyl nucleus A can be substituted, e.g., by chlorine, bromine, the methyl or methoxy group.

The acid amide group or the ring-closed acid imide group can be present singly or twofold.

In the acyl radical of the formula III of the acid amide group, R, represents a lower alkyl radical having one to four carbon atoms, a monoor binuclear aryl radical, e.g., the phenyl radical, a phenyl radical substituted by halogen, alkyl, alkoxy or acylamino groups, the diphen yl or the naphthyl radical; furthermore, R, can represent an heterocyclic radical such as, e.g., acid derivatives of pyridine, or a hydroaromatic radical. in the acyl radical of the formula III, R, can also represent, e.g., the radical OR. or -NHR The acyl group can also he, therefore, an aromatic or an aliphatic urethane or urea group having preferably one to four carbon atoms.

Suitable acylated aminosalicylic acid radicals of the formula II, according to the invention, are for example the following:

HO- HO Cl no-O-mr-c o-Qcmn.

In formula ll of the salicylic acid ester, the acid amide group can also be ring-closed, i.e., R, and R, can together form an optionally fiveor six-membered cyclic carbimide radical, whereby the cyclic carbimide radical can be, e.g., an optionally substituted phthalimido group or a pyridine-di-carboxylic acid imide group.

The anthraquinone pigments, according to the invention, have an outstanding fastness to migration, solvents and cross-lacquering, in addition to an excellent fastness to weather and light. In general, they possess a good texture and can often be used in the form of their crude product. If necessary or desirable, the crude products can be converted, by grinding or kneading, into a finely dispersed form. Grinding auxiliary agents are thereby advantageously used, such as inorganic and/or organic salts in the presence or absence of organic solvents. An improvement in the properties can also frequently be achieved by heating the crude pig- 5 ments in hot organic solvents. After grinding, the auxiliary agents are removed in the usual manner, soluble inorganic salts being removed, for example. with water and water-insoluble organic auxiliaries, e.g., by steam distillation. Reprecipitation from sulphuric acid also frequently suffices to obtain a deeply-colored, finely dispersed, transparent pigment fiber.

Particularly preferred compounds falling under formula I are those in which X represents Hal represents chlorine or bromine, m represents from 0 to 4, a first of Y,, Y, and Y, represents the same as X-NH, benzoylamino, chloro-benzoylamino, or hydrogen, and the second and the third thereof represent hydrogen; each of Y,, Y,, Y and Y, is hydrogen or chlorine.

MOst preferred are those pigments falling under formula I, wherein X represents (HaDm YiO NH2 i l wherein Y, to 1, have the meaning given in fonnula l, by

reaction with a compound yielding the salicylic acid radical of the formula II. Suitable as a compound yielding the salicylic acid radical are the salicylic acids or salicylic acid halides corresponding to the salicylic acid radicals of the formula II. The amide formation can also proceed by way of the radical of the formula II with the laminoanthraquinone, corresponding to a reamidation reaction.

Moreover, the acylation can be performed with an aliphatic, aromatic, hydroaromatic or heterocyclic (ortho) dicarboxylic acid, a dicarboxylic acid anhydride or -halide to the carbimide compound.

Suitable for the amide formation, according to the invention, are for example the following 1 -aminoanthraquinones l -aminoan thraquinone l -amino-4-chloroant hraquinone l-amino-5-chloroanthraquinone l -amino-6,7-dic hloroanthraquinone l-amino-5,6,7,8-tetrachloroanthraquinone l -amino-Z-methylanthraquinone l-amino-6,7-dimethylanthraquinone l -arnino-2,4-dibromoanthraquinone l -amino-4,5-dimethoxyanthraquinone l -amino-5,S-dirnethoxyanthraquinone 1 -arnino-4-methoxyanth raq uinone 1 -amino-4-methoxy-5 -c hloroanthraquinone l -amino-2-methyl-4-chloroanthraq uinone l -amino-4- benzoylaminoanthraq uinone In the above given l-aminoanthraquinones, a second amino substituent can optionally be present. This second amino radical can be in four--, fiveor eight-position and can be reacted, for example, with a further salicylic acid radical of the formula II, or with an unsubstituted or substituted benzoic acid. According to the invention, the acylation of the laminoanthraquinone in the l-amino position is always effected by a salicylic acid derivative yielding the salicylic acid radical of the formula II.

The production of the pigments of the formula 1, according to the invention, can for example also be achieved by performing the acylation of the aminoanthraquinones with salicylic acids or -chlorides containing nitro groups, and then further acylating the obtained compounds, following the reduction of the nitro group(s) to the amino group(s) after the first acylation, in accordance with the explanations given above for the pigments of formula 1.

The new pigments of the anthraquinone series are suitable for the pigmenting of polymeric organic material, e.g., in printing inks for the printing industry, in paints having an oily base such as linseed-oil paints, or with an aqueous base such as dispersion paints, or in lacquers of varying kinds such as in nitrolacquers or stoving lacquers, having in the latter case, e.g., an alkyd resin or acryl resin base. They can also be used for the spinning-dyeing of viscose or cellulose acetate, for the pigmenting of plastics such as polyethylene, polystyrene, polyvinyl chloride, whereby the latter can also contain softeners, also for the pigmenting of cellulose esters, curable resins or for the pigmenting of rubber. They are also applicable for the dyeing of paper pulp or for the coating of webs, e.g., in the production of laminated paper.

The following examples illustrate the invention without limiting it in any way. All temperatures are given in degrees Centigrade.

EXAMPLE 1 22.3 g of l-aminoanthraquinone and 46.3 g of 2- hydroxy-S-tetrachlorophthalimido-l-benzoic acid are heated with 500 ml of benzoic to l05-l 10. Into the yellow suspension are then added, while stirring well and within 1 V4 hours, l3.56 g of thionyl chloride, dissolved in 50 ml of nitrobenzene. When the formation of hydrochloric acid has subsided after about 30 minutes, the suspension is heated for 2 hours to l40l 45 and, to complete the reaction, for a further 20 minutes to l60l65. After cooling to 1 10, the precipitated yellow product is filtered off, washed with nitrobenzene and then with alcohol, and dried at in vacuo. By this means are obtained 6 1.5 g of a greenish-yellow pigment of the above stated formula, which has a very good fastness to cross-lacquering, migration, light and weather.

If the 2-hydroxy-5-tetrachlorophthalirnidol -benzoic acid is replaced by equimolecular amounts of 2- hydroxy-5-(4'-chloroor 4-nitrophthalimido)lacid, 2-hydroxy-5-phthalimido-l-benzoic acid 2-hydroxy-4- tetrachlorophthalimido-l-benzoic acid, or Z-hydroxy- 4-phthalimido-l-benzoic acid, with the procedure being otherwise the same, then pigments are obtained having similar fastness properties to those stated above.

Furthennore, if the 22.3 g of l-aminoanthraquinone are replaced by equimolecular amounts of one of the aminoanthraquinones listed in the following table I, using otherwise the same procedure, then pigments are obtained having similar fastness properties and with the shades given in column 3 of the table.

TABLE] Shade in P p Ex. Aminoanthraquinone printing 2 l-amino-4-chloroanthraquinone yellow 3 l -amino-5-ch loroanthraquinone yellow 4 l -amino-6,7-dichloroanthraquinone reddishyellow 5 l -arnino-S ,6,7 .8tetrachlororeddishanthraquinone yellow 6 l-arnino-2-methylanthraquinone reddishyellow 7 l -amino-2 ,4-dibrornoanthraquinone yellow 8 l-amino-4-methoxyanlhraquinone orange 9 l-amino-4-methoxy-5-chlom orange anthraquinone l 0 l -amino-2-methyl-4-chlororeddisl'| anthraquinone yellow l l l-arnino-4-(4'-chlorobenzoyl)- orange aminoanthraquinone I la l-arnino-5-(4-chlorobenzoyl)- yellow aminoanthraquinone l lb l ,4-diamino-Z,3-dichloroanthraquinone orange EXAMPLE l2 0 ll C 110- 4.76 g of 1,4-diaminoanthraquinone and l 1.9 g of 2- hydroxy-S-phthalimido-l-benzoic acid are suspended in 250 ml of nitrobenzene and heated to lS-l To this suspension are then added dropwise within 2 hours, 5.22 g of thionyl chloride, dissolved in ml of nitrobenzene. While stirring well, it is then heated for 3 hours to ll55 and then for a further 15 minutes to l-l After cooling to 80, the orange-red colored product is filtered off, washed with nitrobenzene, alcohol and acetone and dried. By this means are obtained 13.4 g of a reddish-yellow pigment of the above given formula having an excellent fastness to crosslacquering, migration and light.

Pigments exhibiting similarly good fastness properties are obtained if, using otherwise the same procedure, the .9 g of Z-hydroxy-S-phthalimido-lbenzoic acid is replaced by the equimolecula: amount of 2-hydroxy-4-phthalimidol -benzoic acid, Z-hydroxy- S-hexahydrophthalimido-l-benzoic acid, Z-hydroxy-S- (3'-pyridinoylamido)-l-benzoic acid. 2-hydroxy-5-(2'- furanoylamido)-l-benzoic acid or 2-hydroxy-5-( '.8'- naphthalimido)- l -benzoic acid.

EXAMPLE13 O NII- C O- 8.92 g of l-aminoanthraquinone and l2.82 g of 2- hydroxy-5-( 4'-cl'florobenzoylamino l -benzoic acid are heated with 200 ml of nitrobenzene to -9S. At this temperature is slowly added dlopwise, a solution of 5.23 g of thionyl chloride in 20 ml of nitrobenzene. After this addition has been made, the greenish-yellow suspension is heated within 30 minutes to l30-l35 and then stirred for a further 3 hours at this temperature. After cooling to 90, the product is filtered ofl, washed with nitrobenzene, alcohol and acetone and dried in vacuo at Sir-90. The yield is 14.6 g. The greenish-yellow pigment of the above given formula :1; a very good fastness to cross-lacquering and to Example Sharla in paper No. llydroxybonzolc acid printing no m roonlsli yellow HO0C- -N1I-o0-c1 H0 o 3000- N1Ic0- cm 16 Yellow.

FNil-4: o-Q- 0 cm HO O C-- V 17 Cl Greenlsh yellow.

HO 0 C -NH-C 0-NH-C'1Hs Iill-IC 0- Br H000 Cl 19 (IJH; Reddish yellow.

Ho/ HOOO\/ NH--C o-Q-oom HOOC\/ -NHC 0NH-C 0-011,

H0-- NHC o-un-c o-Q-cn H0O C-\/ 22 Greenish allow.

'l'uhlc Continued Fxamplt Sluidu in pnpvr No. llydroxybenzoic acid printing 23 V Do.

HO- I 3000- NH-CO-NO1 24 Yellow.

nooc- NH-C ONH Pigments having similarly good fastness properties are obtained if the 2-hydroxy-5-(4'- chlorobenzoylamino)-l-benzoic acid, given in the example, is replaced by equimolecular amounts of a substituted 2-hydroxy-l-benzoic acid listed in table II. The shades of color in the paper printing are given in column 3 EXAMPLE 26 formula are thus obtained, which has a very good fastness to cross-lacquering and light.

EXAMPLE 27 0 C1 H0- s -01 c I v! r) NII in 8.55 g of l-amino-4-benzoylaminoanthraquinone and 11.6 g of Z-hydroxy-S-tetrachlorophthalimido-lbenzoic acid are heated with 200 ml of nitrobenzene to l05l l0. Into the orange-red suspension are then added, within 1 A: hours, 3.4l g of thionyl chloride dissolved in 25 ml of nitrobenzene. After the evolution of hydrochloric acid has finished, the suspension is heated for 3 hours to l45-l50. It is then cooled to 100 and the orange-red product of the above given formula is filtered 011'. It is washed with nitrobenzene and then with ethanol and dried.

By this means are obtained 15 g of an orange-red pigment which has a very good fastness to cross-lacquering and to light.

EXAMPLE 28 Ill) Within 2 hours, 8.92 g of thionyl chloride dissolved in 30 ml of nitrobenzene are added dropwise to a suspension heated to -95 of 7.15 g of 1,5- diaminoanthraquinone and 14 g of Z-hydroxy-S- acetylamino-l-benzoic acid in 250 ml of nitrobenzene. The suspension is maintained for 1 hour, while stirring well, at -l00 and then heated for a further 3 hours to l40l45. After cooling to the reddish-yellow product is filtered off, washed with nitrobenzene and alcohol and dried. By this means are obtained 16 g of a reddish-yellow pigment of the above given formula, which has a very good fastness to cross-lacquering, migration and light.

If, in the above example, the 14 g of 2-hydroxy-5- acetylamino-l-benzoic acid are replaced by 18.5 g of 2- hydroxy-S-benzoylamino-l-benzoic acid, with otherwise the same procedure, then likewise is obtained a reddish-yellow pigment having similar properties.

EXAMPLE 29 3.75 g of 2'-hydroxy-3',5'-diaminobenzoy1-1- aminoanthraquinone with 3.85 g of p-chlorobenzoyl chloride in 150 ml of freshly distilled o-dichlorobenzene are refluxed for 7 hours. A yellow precipitate is formed which is filtered off at 150. After the residue has been washed with o-dichlorobenzene, alcohol and acetone and then dried, 3 g of a yellowish-brown pigment are obtained having a very good fastness to crosslacq uering.

The 2 '-hydroxy-3 ',5 -diaminobenzoyl-1-aminoanthraquinone is obtained by condensation of 2- hydroxy-3,5-dinitrobenzoic acid with laminoanthraquinone in nitrobenzene in the presence of thionyl chloride, and by subsequent reduction of the nitro groups by means of sodium dithionite in water-alcohol in the presence of soda.

If, in this example, the p-chlorobenzoyl chloride is replaced by equimolecular amounts of o-ch|oro, or methyl or p-methylbenzoyl chloride, with the procedure otherwise as described above, then likewise are obtained yellowish-brown pigments having good fastness to cross-lacquering.

EXAMPLE 30 5.18 g of bis-(2'-hydroxy-$-'-aminobenzoyl)-1,5- diaminoanthraquinone are refluxed for 3 hours with 4.87 g of o-phthalic acid dichloride in 200 mlof freshly distilled o-dichlorobenzene. The formed yellow precipitate is filtered off at 150, Washed with odichlorobenzene, alcohol and acetone and dried. By this means are obtained 5.7 g of a yellow powder which, after grinding with salts, yields a reddish-yellow 12 pigment having a good fastness to light, cross-lacquering and migration.

The bis-( 2-hydroxy-5 '-aminobenzoyl )-1 ,S-diaminoanthraquinone is obtained by condensation of 2- hydroxy-S-nitrobenzoic acid with 1,5-

diaminoanthraquinone in nitrobenzene in the presence of thionyl chloride and by subsequent reduction of the nitro groups by means of sodium dithionite in water-alcohol in the presence of soda.

Reddish-yellow pigments having similarly good properties are obtained if, in this example, the o-phthalic acid dichloride is replaced by equimolecular amounts of tetrachlorophthalic acid dichloride, benzoyl chloride, p-chlorobenzoyl chloride or p-methylbenzoyl chloride.

EXAMPLE31 no 0 N11 in i] 1 \CU i T ll]:

27.25 g of 1,4-diamino-2-chloroanthraquinone and 46.3 gof 2-hydroxy-S-tetrach1orophthalimido-1-benzoic acid are heated with 500 g of nitrobenzene to 105l Into the suspension are introduced, while stirring, 13.56 g of thionyl chloride, dissolved in ml of nitrobenzene. The suspension is then heated for two hours to 140l45. The red suspension is filtered off hot, the residue washed with nitrobenzene and alcohol 50 and dried. This produces 63 g of a red pigment which has a very good fastness to cross-lacquering.

EXAMPLE 3 2 4.76 g of 1,8-diaminoanthraquinone and 1 1.9 g of 2- hydroxy-S-phthalimido-1benzoic acid are suspended in 250 ml of 1,2-dichlorobenzene and heated to -110. Into this suspension are added dropwise within 1 hour, 5.22 g of thionyl chloride, dissolved in 20 ml of nitrobenzene. While stirring well, the suspension is then heated for 3 hours to l$l56 and for a further 15 minutes to l70-l75. After cooling to 80, the reddish-yellow product is filtered off, washed with 1,2-dichlorobenzene, alcohol and acetone, and dried. By this means are produced [2 g of a yellow pigment of the above given formula, which has an excellent fastness to cross-lacquering, migration and light.

EXAMPLE 33 40 g of the pigment produced according to Example 27, 360 g of hydrate of alumina, 600 g of linseed oil varnish of medium viscosity and 2 g of cobalt linoleate are mixed on a three-roller mill and ground. A printing ink is obtained which produces orange-red paper printings which have an excellent fastness to light.

EXAMPLE 34 To [00 g of a stoving lacquer consisting of 58.5 g of a 60 percent solution of a coconut alkyd resin in xylene, 23 g of a 65 percent solution of a melamine gum-lac in butanol, 17 g of xylene and 1.5 g of butanol, is added l g of the pigment produced according to example 13 and 5 g of titanium dioxide. The mixture is ground for 48 hours in a ball mill and the thus pigmented lacquer is sprayed on to a cleaned metal surface. After stoving at 120, a yellow dyeing is obtained having a good fastness to light, cross-lacquering and to weather.

EXAMPLE 35 67 g of polyvinyl chloride powder (suspension polymerisate), 33 g of dioctylphthalate, 2 g of dibutyl tin dilaurate, 0.3 g of a stabilizer based on phosphate and 0.7 g of the pigment, produced according to example l by condensation of l-amino-anthraquinone and Z-hydroxy-S-tetrachlorophthalimidel -benzoic acid, are mixed together and treated for minutes on the mixing rollers which are heated to 160. A sheet with a thickness of 0.4 mm is subsequently produced on a calendering machine. it is dyed in a pure greenish-yellow shade, whereby the dyeing is resistant to heat and is fast to migration.

We claim:

1. A pigment of the formula wherein Hal is chlorine or bromine,

m is an integer ofO to 4, and

the substituents Y to Y,, represent hydrogen, chlorine, bromine, methyl, or methoxy with the proviso that 3 to 7 of the Y substituents represent hydrogen, 0 to 2 of the Y substituents represent methyl, methoxy or bromine, and with the further proviso that O to l of the substituents Y Y, and Y further represents NH,, benzoylamino,

chlorobenzoylamino or the radical 2. A pigment as defined in claim 1, which is of the 3. A pigment as defined in claim 1, which is of the formula 4. A pigment as defined in claim 1, which is of the formula O IIIH-CO- II n 5. A pigment as defined in claim I, which is of the formula 6. A pigment as defined in claim 1, which is of the formula 7. A pigment as defined in claim 1 wherein one of Y and Y; represents benzoylamino,

chlorobenzoylamino, the radical 10 or hydrogen and the second and third thereof represent chlorobenzoylamino and the other represents hydrogen, and each of Y. and Y represent hydrogen or chlorine. 

2. A pigment as defined in claim 1, which is of the formula
 3. A pigment as defined in claim 1, which is of the formula
 4. A pigment as defined in claim 1, which is of the formula
 5. A pigment as defined in claim 1, which is of the formula
 6. A pigment as defined in claim 1, which is of the formula
 7. A pigment as defined in claim 1 wherein one of Y4, Y5 and Y8 represents benzoylamino, chlorobenzoylamino, the radical or hydrogen and the second and third thereof represent hydrogen, and each of Y2, Y3, Y6 and Y7 is hydrogen or chlorine.
 8. A pigment as defined in claim 1 wherein Y2, Y3 and Y8 represent hydrogen, one of Y4 and Y5 represents benzoylamino or chlorobenzoylamino and the other represents hydrogen, and each of Y6 and Y7 represent hydrogen or chlorine. 